CN101511441B - Method for purifying ionic liquids - Google Patents
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Abstract
Description
技术领域 technical field
本发明涉及一种根据权利要求1前序部分所述的净化离子液体的方法。The invention relates to a method for purifying ionic liquids according to the preamble of claim 1 .
背景技术 Background technique
WO2006/061188教导了为了净化离子液体，使离子液体自其熔体部分结晶和将在所述结晶过程中形成的结晶物与剩余熔体分离。在这点上所述结晶可以动态或静态地进行。根据WO2006/061188所有类型的已知离子液体都可以通过部分结晶来净化。WO 2006/061188 teaches the partial crystallization of ionic liquids from their melts and the separation of the crystals formed during said crystallization from the remaining melt in order to purify ionic liquids. The crystallization in this regard can be performed dynamically or statically. All types of known ionic liquids according to WO2006/061188 can be purified by partial crystallization.
DE-A-10 2004 027 196涉及一种使分子量＞1000g/mol的聚合物和生物聚合物在离子液体的帮助下结晶的方法。根据DE-A-10 2004 027196的方法，所述聚合物和生物聚合物被溶解在一种溶剂混合物中，其中的一或多种溶剂为离子液体。离子液体的比例大于50体积％或优选地大于80体积％。现在，为实现期望聚合物或生物聚合物的结晶，所述方法的基本原理是改变它们在所述溶剂混合物中的溶解度。在这点上，根据第一种变体，制备了待结晶的化合物在离子液体中的饱和溶液。将此溶液放入含有特定浓度的絮凝剂的气体空间中。随着时间的过去所述溶液开始随所述絮凝剂从气体空间中慢慢饱和析出直至达到平衡。如果所述絮凝剂在所述离子液体中的平衡浓度为足以析出，则在所述离子液体中可发现所述待结晶的聚合物或生物聚合物的晶体。DE-A-10 2004 027 196 relates to a process for the crystallization of polymers and biopolymers with a molecular weight > 1000 g/mol with the aid of ionic liquids. According to the method of DE-A-10 2004 027196, the polymers and biopolymers are dissolved in a solvent mixture, one or more of which are ionic liquids. The proportion of ionic liquid is greater than 50% by volume or preferably greater than 80% by volume. Now, to achieve the crystallization of desired polymers or biopolymers, the basic principle of the method is to modify their solubility in the solvent mixture. In this regard, according to a first variant, a saturated solution of the compound to be crystallized in an ionic liquid is prepared. This solution is placed in a gas space containing a specific concentration of flocculant. Over time the solution begins to slowly saturate out of the gas space with the flocculant until equilibrium is reached. Crystals of the polymer to be crystallized or biopolymer may be found in the ionic liquid if the equilibrium concentration of the flocculant in the ionic liquid is sufficient for precipitation.
根据第二种变体，所述待结晶的聚合物几乎不溶于所述离子液体，但其能充分溶于一种能与所述离子液体混合的助溶剂中。所述聚合物现在被溶解在离子液体与助溶剂的混合物中并制得饱和溶液。然后使此混合物进入气态助溶剂贫乏的所述气体空间中。助溶剂从所述含离子液体的混合物中慢慢蒸发，留下具有期望聚合物晶体的离子液体。上述方法并未涉及离子液体的净化，而是涉及使用离子液体净化聚合物。这些离子液体在整个方法过程中以液体聚集态存在。According to a second variant, the polymer to be crystallized is practically insoluble in the ionic liquid, but is sufficiently soluble in a co-solvent that is miscible with the ionic liquid. The polymer is now dissolved in a mixture of ionic liquid and co-solvent and a saturated solution is made. This mixture is then passed into the gas space depleted of gaseous cosolvent. The co-solvent slowly evaporates from the ionic liquid-containing mixture, leaving the ionic liquid with the desired polymer crystals. The methods described above do not relate to the purification of ionic liquids, but to the purification of polymers using ionic liquids. These ionic liquids are present in liquid aggregates throughout the process.
离子液体的一个已知问题在于它们通常难以结晶，因为它们具有高度的不对称性。这阻碍了结晶或使其不可能发生。同时，许多离子液体显示复杂的相特性。其结果是在冷却时许多离子液体形成玻璃状结构。离子液体往往具有高粘度，此外趋于过冷直至发生玻璃状凝固。A known problem with ionic liquids is that they are often difficult to crystallize because of their high degree of asymmetry. This hinders or makes it impossible for crystallization to occur. At the same time, many ionic liquids display complex phase properties. As a result, many ionic liquids form glass-like structures on cooling. Ionic liquids tend to have high viscosities and moreover tend to be supercooled until glassy solidification occurs.
某些离子液体如EMIM氯化物形成两种结晶变体，其中高熔融变体是更利于分离的晶体形式。由于趋向于过冷，在所述高熔融变体的凝固点以下不形成晶体。只有在超过所述转变温度之后低熔融变体才开始结晶。Certain ionic liquids such as EMIM chloride form two crystalline modifications, with the high-melting modification being the more favorable crystal form for separation. Crystals do not form below the freezing point of the high melting variant due to the tendency to supercool. Crystallization of the low-melting variant begins only after the transition temperature is exceeded.
只有在降到所述相转变温度以下之后，低熔融变体才开始结晶。在极端情形下，在所述冷却过程中甚至将温度降到远低于所述相转变温度也根本不会发生晶体的形成。于是这样一种液体非晶态地凝固。Only after falling below the phase transition temperature does the low melting variant begin to crystallize. In extreme cases, crystal formation does not occur at all during the cooling process even down to temperatures well below the phase transition temperature. Such a liquid then solidifies amorphously.
液体粘度很高时，分子材料传输进行地很慢，由此极小的晶体生长。对于随后晶体与剩余熔体的分离来说，这种生长是不利的。这种不利的生长可以通过减缓晶体的生长速度来阻止，因为液体被更慢地冷却。但是这在工业过程中大抵是不受欢迎的。When the viscosity of the liquid is high, molecular material transport proceeds very slowly, whereby extremely small crystals grow. This growth is disadvantageous for the subsequent separation of the crystals from the remaining melt. This unfavorable growth can be prevented by slowing down the growth rate of the crystals as the liquid is cooled more slowly. But this is largely undesirable in industrial processes.
在本发明的范围内，具有有机化合物的盐应被理解为离子液体，其在150℃以下且优选地100℃以下以液态存在。在WO2006/061188和DE-A-10 2004 027 196中列出了大量可能的离子化合物。因此WO2006/061188和DE-A-10 2004 027 196的内容被通过引用包含在本申请之中。Within the scope of the present invention, salts with organic compounds are to be understood as ionic liquids which exist in the liquid state below 150° C. and preferably below 100° C. A large number of possible ionic compounds are listed in WO2006/061188 and DE-A-10 2004 027 196. The contents of WO2006/061188 and DE-A-10 2004 027 196 are therefore incorporated by reference into the present application.
发明内容 Contents of the invention
基于上述现有技术，本发明的目的在于提供一种基本上避免了上述缺陷的改善的离子液体净化方法。本发明的另一目的在于提供一种可以更有效地净化以不同形态结晶的化合物的改善的净化方法。Based on the above-mentioned prior art, the object of the present invention is to provide an improved ionic liquid purification method which substantially avoids the above-mentioned drawbacks. Another object of the present invention is to provide an improved purification method which allows more efficient purification of compounds crystallized in different morphologies.
根据本发明此目的可以由根据权利要求1前序部分所述的方法达到，即，向离子液体中首先加入一定量的至少一种夹带剂物质，然后才被结晶。通常夹带剂物质应被理解为在分离过程的意义上能对固相与液相之间的多余组分的分布产生积极影响的夹带剂。夹带剂物质的专门添加还具有能降低液体(熔体)粘度并从而(既通过扩散又通过对流)强化材料传输的优点。由此强化了分离效果，因为对于给定的生长速度来说产生了更大的晶体，这导致了好得多的固/液分离。This object is achieved according to the invention by the method according to the preamble of claim 1 in that a certain amount of at least one entrainer substance is first added to the ionic liquid and only then crystallized. Entrainer substances are generally to be understood as entrainers which, in the sense of a separation process, have a positive influence on the distribution of excess components between solid and liquid phases. The specific addition of entrainer substances also has the advantage of being able to reduce the liquid (melt) viscosity and thereby enhance material transport (both by diffusion and by convection). The separation effect is thereby enhanced, since larger crystals are produced for a given growth rate, which leads to a much better solid/liquid separation.
有利地，使用与离子液体或与离子液体中所含污染物具有相似结构特性的化合物作为夹带剂物质。例如，在EMIM氯化物(氯化1-乙基-3-甲基咪唑)结晶时可以添加1-甲基咪唑。由此可以对所述污染物在液体(熔体)与结晶之间的分布产生积极影响。这表现为更少的污染物被引入结晶中上。Advantageously, compounds having similar structural properties to the ionic liquid or to the contaminants contained in the ionic liquid are used as entrainer substances. For example, 1-methylimidazole can be added during crystallization of EMIM chloride (1-ethyl-3-methylimidazole chloride). This can have a positive influence on the distribution of the contaminants between liquid (melt) and crystallization. This manifests itself as fewer contaminants being introduced into the crystallization.
有利地，使用与离子液体中所含污染物具有相似结构特性的化合物作为夹带剂物质。这样一种夹带剂物质的专门添加的优点在于，例如，污染物的熔解度得以提高且它们由此更多地保留在液体中。通常，也可以添加化合物(夹带剂)的混合物来作为夹带剂。Advantageously, compounds having similar structural properties to the contaminants contained in the ionic liquid are used as entrainer species. The advantage of such a dedicated addition of entrainer substances is, for example, that the solubility of the contaminants is increased and they are thus retained more in the liquid. Often, mixtures of compounds (entrainers) can also be added as entrainers.
有利地，添加到所述被污染的离子液体中的夹带剂物质的量按重量计小于所述离子液体重量的50％，优选地小于所述离子液体重量的30％，且特别优选地小于所述离子液体重量的10％。这意味着在实践中本领域普通技术人员通常只需添加能实现污染物溶解度的期望提高和/或一般而言分离效果的期望提高的量的夹带剂物质。由于夹带剂物质的添加，离子液体的熔点通常被降低，使得在某些情形下，进行所述结晶过程需要更多的能量。Advantageously, the amount of entrainer species added to the contaminated ionic liquid is less than 50% by weight of the ionic liquid, preferably less than 30% by weight of the ionic liquid, and particularly preferably less than the 10% of the weight of the ionic liquid. This means that in practice a person of ordinary skill in the art usually only needs to add the amount of entrainer species that achieves the desired increase in contaminant solubility and/or in general the desired increase in separation efficiency. Due to the addition of entrainer species, the melting point of the ionic liquid is generally lowered, so that in some cases more energy is required to carry out the crystallization process.
相似结构特性应理解为例如夹带剂物质具有与离子液体相同的基本结构或相似极性，从而其溶解度得以提高，但其本身通常不是离子性的。Similar structural properties are understood to mean, for example, that the entrainer substance has the same basic structure or a similar polarity as the ionic liquid, so that its solubility is enhanced, but is generally not itself ionic.
已知的与待净化离子液体中所含污染物具有相似结构特性的传统溶剂也可被用作夹带剂物质。这类溶剂例如有甲醇、乙醇、异丙醇、丁醇、戊烷、己烷、丙酮、甲乙酮、呋喃、二甲亚砜、甲苯、苯、乙酸甲酯、乙酸乙酯、或上述溶剂中的一或多种的混合物。Conventional solvents known to have similar structural properties to the contaminants contained in the ionic liquid to be purified can also be used as entrainer species. Such solvents are, for example, methanol, ethanol, isopropanol, butanol, pentane, hexane, acetone, methyl ethyl ketone, furan, dimethyl sulfoxide, toluene, benzene, methyl acetate, ethyl acetate, or A mixture of one or more.
有利地，结晶在正压力下进行且可溶于离子液体的气体如CO2、CH4和N2被用作夹带剂物质。使用可溶气体的优点是所述气体可被很容易地再驱除。也可以使用可压缩的气体如甲烷、乙烷、丙烷、正丁烷或卤代烃如氯代甲烷在离子液体中作夹带剂物质。同样，这些气体也可在稍微升高的温度下被很容易地再驱除。Advantageously, crystallization is performed under positive pressure and ionic liquid soluble gases such as CO2 , CH4 and N2 are used as entrainer species. The advantage of using a soluble gas is that the gas can be easily repelled. Compressible gases such as methane, ethane, propane, n-butane or halogenated hydrocarbons such as methyl chloride can also be used as entrainer substances in ionic liquids. Likewise, these gases can be easily re-expelled at slightly elevated temperatures.
夹带剂物质可被用于离子液体的静态结晶和动态结晶。在静态结晶时没有用外力对液相施加对流且晶体形成在设置于结晶器内的冷却表面上。Entrainer species can be used for both static and dynamic crystallization of ionic liquids. In static crystallization no external force is applied to convect the liquid phase and crystals are formed on cooling surfaces provided in the crystallizer.
在动态结晶时，液相被搅拌或循环。已知的动态结晶方法有悬浮结晶、完全流通管型结晶或降膜结晶。上述结晶方法例如在US5504247和WO2006/061188中有更详细的记述，其内容特此通过引用并入。In dynamic crystallization, the liquid phase is stirred or circulated. Known dynamic crystallization methods include suspension crystallization, complete flow tubular crystallization, or falling film crystallization. The above-mentioned crystallization methods are described in more detail, for example, in US5504247 and WO2006/061188, the contents of which are hereby incorporated by reference.
原则上可以使用单步或多步结晶方法来进行离子液体的净化。有利地，在多个步骤中以分级结晶进行所述结晶。各个结晶级定义出期望化合物的不同纯净度。在最低结晶级中，污染物的浓度最高；在最高结晶级中，期望的化合物以净化后的形式存在，其中污染物被脱除得最多。在多步结晶方法中，某一结晶级的未结晶残余物被输入低一级的结晶级中。某一结晶级中析出的晶体优选地被渗出且俘获的渗出相被重新输入同一级的工作混合物中或被分成两部分，其中第一部分被添加到该结晶级的残余物中，而第二部分被添加到同一级的进料混合物中。剩余下来的结晶物随后被熔融和添加到高一级的结晶级中。原则上可以依次排列任意数目的结晶级。在实践中使用的结晶级应多至使最高结晶级具有期望的纯度。Purification of ionic liquids can in principle be performed using single- or multi-step crystallization methods. Advantageously, said crystallization is carried out as fractional crystallization in several steps. Each crystallization grade defines a different degree of purity of the desired compound. In the lowest crystallization grade, the concentration of contaminants is highest; in the highest crystallization grade, the desired compound exists in a purified form, where the contaminants are most removed. In a multi-stage crystallization process, the uncrystallized residue of a certain crystallization grade is fed into a lower crystallization grade. The precipitated crystals in a certain crystallization grade are preferably exuded and the trapped exudated phase is reintroduced into the working mixture of the same grade or divided into two parts, wherein the first part is added to the residue of the crystallization grade and the second The two fractions are added to the feed mixture at the same stage. The remaining crystalline material is then melted and added to a higher crystalline grade. In principle, any number of crystalline stages can be arranged one behind the other. In practice the crystallization grades used should be as many as are required so that the highest crystallization grade has the desired purity.
污染物富集在最低结晶级的残余物中。在这一情形下，所述残余物中包含夹带剂物质及其它污染物。Contaminants are concentrated in the lowest crystalline grade residue. In this case, the residue contains entrainer species and other contaminants.
实施例Example
通过添加1-甲基咪唑作为夹带剂物质可以提高1-乙基-3-甲基咪唑、1-丁基-3-甲基咪唑、1-己基-3-甲基咪唑或1-辛基-3-甲基咪唑的氯化物或溴化物的净化效果。在此，所述结构相似性存在于夹带剂物质的咪唑环与咪唑鎓阳离子之间。不过，通过添加例如作为夹带剂物质与上述离子化合物中的乙基、丁基、己基或辛基具有结构亲和性的辛烷也可达到类似的效果。进一步的例子有乙基吡啶或甲基吡啶的氯化物或溴化物，它们的净化效果可以通过添加吡啶来提高。另一例子是由咪唑鎓作为阳离子和甲苯硫酸根作为阴离子构成的离子液体，其净化效果可通过添加苯、二甲苯、甲苯或这类物质的混合物来提高。在此例中夹带剂物质与所述甲苯硫酸根阴离子具有结构相似性。1-ethyl-3-methylimidazole, 1-butyl-3-methylimidazole, 1-hexyl-3-methylimidazole or 1-octyl- Purification effect of chloride or bromide of 3-methylimidazole. Here, the structural similarity exists between the imidazole ring of the entrainer substance and the imidazolium cation. However, a similar effect can also be achieved by adding, for example, octane, as an entrainer substance, which has a structural affinity with the ethyl, butyl, hexyl or octyl groups in the above-mentioned ionic compounds. Further examples are the chlorides or bromides of ethylpyridine or picoline, the purifying effect of which can be enhanced by adding pyridine. Another example is an ionic liquid composed of imidazolium as cation and toluene sulfate as anion, the purification effect of which can be enhanced by adding benzene, xylene, toluene or a mixture of such substances. The entrainer species in this case has structural similarity to the toluene sulfate anion.
本发明的主题还在于根据权利要求17前序部分所述的方法，特征在于所述液体或所述液体物质的一部分被冷却到一定程度以至于低熔融的形态结晶，所述低熔融形态的结晶物随后被加热直至所述低熔融形态被转化成另一种高熔融形态，且如此形成的高熔融形态中的籽晶被用于随后发生的结晶中。申请人意外发现，对开始提到的、以玻璃状形式凝固的物质再加热时，低熔融形态仍可以在相转变温度之下开始结晶。因此晶体不是在冷却时产生的，而是在玻璃状凝固之后的加热时才产生的。本发明的方法优点在于全部固体物质被随后以有利于净化的形态结晶。在此方法的一个变体中，所述液体或所述液体物质的一部分被冷却至开始发生玻璃状凝固为止，并因而随后使由此冷却的物质经历加热，其中在所述加热时低熔融形态仍在相转变温度之下结晶。The subject of the invention is also a method according to the preamble of claim 17, characterized in that the liquid or part of the liquid substance is cooled to such an extent that the low-melting form crystallizes, the crystallization of the low-melting form The substance is then heated until the low melting form is converted to another high melting form, and the seeds in the high melting form so formed are used in the crystallization that occurs subsequently. The Applicant has surprisingly found that, on reheating of the aforementioned substances which solidify in glassy form, the low-melting form can still start to crystallize below the phase inversion temperature. Crystals are therefore not formed on cooling, but upon heating following glassy solidification. The method of the invention has the advantage that all solid matter is subsequently crystallized in a form that facilitates purification. In a variant of this method, the liquid or part of the liquid substance is cooled until glassy solidification begins to take place, and thus the thus cooled substance is subsequently subjected to heating, wherein on said heating the low-melting state Still crystallized below the phase transition temperature.
有利地，通过过冷却到转变点之下再随后加热来使低熔融形态结晶。由此可以实现使待获得的组分以期望的晶体形态结晶。本发明的方法可用于任何趋于过冷却且通过不太适合净化的形态的转变可以达到更适合净化的形态的化合物。Advantageously, the low melting form is crystallized by subcooling below the transition point followed by heating. Crystallization of the desired crystal form of the component to be obtained can thus be achieved. The method of the present invention is applicable to any compound which tends to be supercooled and which can be transformed into a form more suitable for purification by transformation of a form less suitable for purification.
下面将参照附图1对本发明进行更详细地描述，该图1是EMIM氯化物的差示扫描量热图。The invention will now be described in more detail with reference to Figure 1 , which is a differential scanning calorimetry diagram of EMIM chloride.
图中显示了EMIM氯化物的冷却曲线和加热曲线。在从100℃冷却到-100℃时，未见到任何会导致结晶的峰。所述曲线发展结果导致发生非晶态的(玻璃状)凝固。The figure shows the cooling and heating curves of EMIM chloride. Upon cooling from 100°C to -100°C, no peaks were seen which would lead to crystallization. The development of the curve results in an amorphous (glassy) solidification taking place.
再加热时，在大约-10℃出现了一个通过结晶产生的大放热峰。在大约70℃和85℃能看到两个由于形态转变和熔融产生的吸热峰。根据本发明，所述加热在超过第二个吸热峰的温度之前被中止，从而高熔融形态未被熔融。此未熔融的晶体物质随后构成用于随后结晶的籽晶。On reheating, a large exothermic peak by crystallization appears at about -10°C. Two endothermic peaks due to morphological transition and melting can be seen at about 70°C and 85°C. According to the invention, the heating is stopped before the temperature of the second endothermic peak is exceeded, so that the high melting form is not melted. This unmelted crystalline material then constitutes the seed crystals for subsequent crystallization.
可使用根据本发明所述的方法净化的离子液体是例如符合通式aAm+bXn-的物质，其中N＝1或n＝2或m＝2，a·m＝b·n，且阳离子选自：The ionic liquid that can be purified using the method according to the present invention is, for example, a substance conforming to the general formula aA m+ bX n- , wherein N=1 or n=2 or m=2, a·m=b·n, and the cation is selected from since:
通式为[R”’][N+]([R’])([R”])[R]的季铵阳离子，A quaternary ammonium cation of the general formula [R"'][N+]([R'])([R"])[R],
通式为[R”’][P+]([R’])([R”])[R]的季鏻阳离子，A quaternary phosphonium cation of the general formula [R"'][P+]([R'])([R"])[R],
通式为[R]N1C＝C[N+]([R’])＝C1的取代或未取代的咪唑鎓阳离子，A substituted or unsubstituted imidazolium cation of the general formula [R]N1C=C[N+]([R'])=C1,
通式为[R]N+1]CC[O]CC1的取代或未取代的吗啉鎓阳离子，A substituted or unsubstituted morpholinium cation of the general formula [R]N+1]CC[O]CC1,
通式为[R]N+]1＝COCC1的取代或未取代的噁唑啉鎓阳离子，A substituted or unsubstituted oxazolinium cation of the general formula [R]N+]1=COCC1,
通式为[R]N+]1＝CC＝CC＝C1的取代或未取代的吡啶鎓阳离子，A substituted or unsubstituted pyridinium cation of the general formula [R]N+]1=CC=CC=C1,
通式为[R]N+]1([R’]CCCC1的取代或未取代的吡咯啉鎓阳离子，Substituted or unsubstituted pyrrolinium cations of the general formula [R]N+]1([R']CCCC1,
通式为[R]N+]1C＝CCC＝N1的取代或未取代的二氢化吡唑鎓阳离子，A substituted or unsubstituted dihydropyrazolium cation of the general formula [R]N+]1C=CCC=N1,
通式为[R]N+]1([R’])N＝CC＝N1或[R]N+]1([R’])C＝NC＝N1的取代或未取代的三唑鎓阳离子，A substituted or unsubstituted triazolium cation of the general formula [R]N+]1([R'])N=CC=N1 or [R]N+]1([R'])C=NC=N1,
通式为[R’]N([R])C(N([R”])[R”])＝[N+]([R”’])[R”’]的取代或未取代的胍鎓阳离子，Substituted or unsubstituted guanidines of the general formula [R']N([R])C(N([R"])[R"])=[N+]([R"'])[R"'] onium cation,
且阴离子选自卤根、四氟硼酸根、RBF3-、六氟磷酸根、RRR’PF3-、磷酸根、PR’PO4-、二氰胺、羧酸根R-COO-、磺酸根R-SO3-、苯磺酸根、甲苯磺酸根、有机磺酸根R-O-SO3-、双(砜)酰亚胺R-SO2-N-SO2-R’、结构为[R’]S([N-])C([R])＝O)(＝O)＝O的酰亚胺、SCN-、CN-、硝酸根、亚硝酸根、氯酸根、高氯酸根，其中R和R’可以相互独立地为线性或支链的含1-20个碳原子的脂族烷基或脂环族烷基或C5-C15-芳基-、C5-C15-芳基-C1-C6-烷基-或C1-C6-烷基-C5-C15-芳基，它们可被卤素原子和/或羟基取代。And the anion is selected from halide, tetrafluoroborate, RBF 3 -, hexafluorophosphate, RRR'PF 3 -, phosphate, PR'PO 4 -, dicyanamide, carboxylate R-COO - , sulfonate R -SO 3 -, benzenesulfonate, toluenesulfonate, organic sulfonate RO-SO 3 -, bis(sulfone)imide R-SO 2 -N-SO 2 -R', the structure is [R']S( [N-])C([R])=O)(=O)=O imide, SCN-, CN-, nitrate, nitrite, chlorate, perchlorate, where R and R' Aliphatic or cycloaliphatic alkyl or C5-C15-aryl-, C5-C15-aryl-C1-C6-alkyl containing 1-20 carbon atoms which can be independently linear or branched - or C1-C6-alkyl-C5-C15-aryl, which may be substituted by halogen atoms and/or hydroxyl groups.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0491558A2 (en) * | 1990-12-18 | 1992-06-24 | Fujitsu Limited | Method and apparatus for two-dimensional measurement of concentration of biological macromolecule solution |
| CN1403443A (en) * | 2002-08-30 | 2003-03-19 | 中国科学院兰州化学物理研究所 | Method of extracting taurine from sodium sulfate |
| CN1562968A (en) * | 2004-03-22 | 2005-01-12 | 浙江大学宁波理工学院 | Method for synthesizing N-substitution pyrrole in ion liquid |
| DE102004027196A1 (en) * | 2004-06-03 | 2005-12-22 | IoLiTec A. Bösmann Dr. T. Schubert oHG | Crystallization of polymers (e.g. polyolefin, polyamide and polyurethane) and biopolymers (e.g. starch, chitin and nucleotide) comprises the utilization of an ionic fluid |
| WO2006045795A2 (en) * | 2004-10-29 | 2006-05-04 | Akzo Nobel N.V. | Processes involving the use of antisolvent crystallization |
| DE102004058907A1 (en) * | 2004-12-07 | 2006-06-08 | Basf Ag | Purification of ionic liquids |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW305830B (en) | 1993-03-26 | 1997-05-21 | Sulzer Chemtech Ag | |
| JP3724864B2 (en) * | 1995-12-01 | 2005-12-07 | 日揮株式会社 | Crystallization method |
| GB9616264D0 (en) * | 1996-08-02 | 1996-09-11 | British Nuclear Fuels Plc | Reprocessing irradiated fuel |
| CA2283670C (en) * | 1998-02-03 | 2011-06-07 | Acep Inc. | Materials useful as electrolytic solutes |
| CN1219770C (en) * | 2001-07-13 | 2005-09-21 | 朱景力 | Process for effectively purifying isoquinoline |
| DE102004003958A1 (en) * | 2004-01-26 | 2005-08-11 | Basf Ag | Production method for ionic liquids |
| DE102004017026A1 (en) * | 2004-04-02 | 2005-10-20 | Merck Patent Gmbh | Ionic liquids with fluoroalkyl trifluoroborate anions |
| GB0423506D0 (en) * | 2004-10-22 | 2004-11-24 | Univ Belfast | Light emitting complex salts |
| DE112005003198B4 (en) * | 2004-12-27 | 2014-02-06 | National Institute Of Advanced Industrial Science And Technology | Ionic liquid |
-
2007
- 2007-09-12 AT AT07800636T patent/ATE522263T1/en active
- 2007-09-12 TW TW096133995A patent/TWI460000B/en not_active IP Right Cessation
- 2007-09-12 EP EP07800636A patent/EP2066416B1/en active Active
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0491558A2 (en) * | 1990-12-18 | 1992-06-24 | Fujitsu Limited | Method and apparatus for two-dimensional measurement of concentration of biological macromolecule solution |
| CN1403443A (en) * | 2002-08-30 | 2003-03-19 | 中国科学院兰州化学物理研究所 | Method of extracting taurine from sodium sulfate |
| CN1562968A (en) * | 2004-03-22 | 2005-01-12 | 浙江大学宁波理工学院 | Method for synthesizing N-substitution pyrrole in ion liquid |
| DE102004027196A1 (en) * | 2004-06-03 | 2005-12-22 | IoLiTec A. Bösmann Dr. T. Schubert oHG | Crystallization of polymers (e.g. polyolefin, polyamide and polyurethane) and biopolymers (e.g. starch, chitin and nucleotide) comprises the utilization of an ionic fluid |
| WO2006045795A2 (en) * | 2004-10-29 | 2006-05-04 | Akzo Nobel N.V. | Processes involving the use of antisolvent crystallization |
| DE102004058907A1 (en) * | 2004-12-07 | 2006-06-08 | Basf Ag | Purification of ionic liquids |
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